JP2001164399A - Method for forming polymer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming polymer films, which is capable of forming film polymer films having excellent concentration uniformity with high resolution directly on substrates having electronic circuit materials without adversely affecting the working characteristics of the electronic circuit materials. SOLUTION: This method for forming the polymer films includes a first stage for bringing the substrates having conductivity into contact with an aqueous electrolyte containing an electrodeposition material and a second stage for forming electrodeposition films by electrochemically depositing the electrodeposition material on the substrates by a change in hydrogen ion concentration. The aqueous electrolyte contains at least either of an ammonium compound and its salt. The ammonium compound or its salt is preferably in the form of a tetraalkyl ammonium compd. or tetraalkyl ammonium hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a polymer film and a method for forming a colored film in a color filter used for various display devices such as a CCD camera and a liquid crystal display device, a display panel, a color image sensor and the like. And a method of forming a colored film (color filter film) directly on a substrate provided with an active element such as a thin film transistor (TFT).

[0002]

2. Description of the Related Art At present, color filters are manufactured by (1) a dyeing method, (2) a pigment dispersion method, (3) a printing method, or the like.
(4) Ink jet method, (5) electrodeposition method, (6) micelle electrolysis method and the like are known, and each has unique features and advantages, but has the following disadvantages. That is, the first dyeing method is frequently used for a color solid-state imaging device (CCD) because of its high transmittance, rich hue, and high technical perfection. However, there are disadvantages that a photolithography step is required for patterning, and that the use of a dye is inferior in light resistance and the number of manufacturing steps is large. The second pigment dispersion method also has a drawback that the cost is high because patterning is performed by a photolithography step and the number of steps is large.
Both the third printing method and the fourth ink jet method do not require a photolithography step, but the former is inferior in resolution and film thickness uniformity, and the latter is liable to cause color mixing between adjacent filter layers, Poor in position accuracy.

The fifth electrodeposition method requires a patterning step by photolithography such as forming a common electrode, and thus has a drawback that the pattern shape is limited and cannot be used for a liquid crystal having a TFT. Further, if a color filter can be integrally formed on the TFT liquid crystal substrate side by an electrodeposition method, there is no need to perform patterning. . Further, since the color filter layer itself is insulative, it cannot be used because the driving voltage increases. The sixth micellar electrolysis method is a kind of electrodeposition method. However, since the oxidation-reduction of ferrocene is used, electrodeposition can be performed at a low voltage and a color filter can be integrally formed directly on the TFT liquid crystal substrate side. But,
The thin film formed by the micellar electrolysis method is inferior in that impurities such as ferrocene and a surfactant are mixed therein and the electrodeposition requires a long time. Furthermore, ferrocene is very expensive and disadvantageous in terms of cost.

In general, a color filter cannot be used merely by forming a color filter layer, but it is necessary to cover the space between filter cells of each color with a black matrix. This is one of the major factors of cost increase.

Therefore, there is a demand for a manufacturing method capable of manufacturing a color filter having high resolution and excellent pattern accuracy at a low cost in a simple process without using a photolithography process. There is an increasing demand for displays capable of displaying information at high resolution, and there is a need for higher definition patterned color filters. Therefore, the present inventors have already applied for a technique capable of stably producing a color filter with high resolution and excellent pattern accuracy by a simple process using a photoelectrodeposition method in order to solve the above problem. (Japanese Patent Application No. Hei 9-13541
0, Japanese Patent Application No. 9-297466, and Japanese Patent Application No. 10-16
No. 2170, Japanese Patent Application No. 10-197564, etc.).

[0006] However, in addition to the above-mentioned electrodeposition method and the like, the photoelectric deposition method also uses an inorganic alkali material (metal cation) in an electrolytic solution used for producing a color filter. Polymer film (color filter film) directly on substrate with material (active element)
When the TFT is to be formed, the electrolyte containing the inorganic metal cations (alkali metal, alkaline earth metal) touches the TFT element to adversely affect the operation characteristics thereof. Therefore, a substrate provided with an electronic circuit material cannot be immersed in an electrolytic solution containing an inorganic alkali material, that is, a color filter having high resolution and excellent pattern accuracy is provided on a substrate provided with an electronic circuit material. It was difficult to form it stably. When an electrodepositable polymer material (electrodeposited material) is dissolved in an aqueous solvent containing an inorganic alkali material to form an electrolytic solution, the dissolution limit pH of the electrodeposited material is about 7.6, and the pigment dispersion Increases the pH by 0.2 or more. For this reason, in order to prevent the re-dissolution phenomenon of the formed polymer film and to form a smooth and strong polymer film, the pH of the electrolytic solution needs to be lower.

Further, increasing the concentration of the electrodeposition material in the electrolytic solution makes it possible to improve the coating on the surface of the pigment and the dispersibility of the pigment when a coloring material such as a pigment is contained. This is advantageous for forming a colored thin film. That is, since the pigment is uniformly dispersed in the electrolytic solution, the color density of the formed colored film is also uniform, and a colored film with less concentration unevenness and less difference in film thickness can be formed. Therefore, as described above, the pH of the electrolyte needs to be low.

As described above, it is possible to further improve the dispersibility of the pigment, effectively prevent the re-dissolution phenomenon of the formed polymer film, and form a smoother and stronger polymer film. Furthermore, even when a substrate provided with an electronic circuit material such as a TFT element is used as an electrodeposition substrate, the pattern accuracy and pattern accuracy can be directly formed on the substrate without considering the adverse effect on the operation characteristics of the electronic circuit material. At present, a method capable of stably forming an excellent polymer film (color filter) has not yet been provided.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention stably forms a high-resolution and high-precision polymer film directly on a substrate provided with an electronic circuit material without considering the adverse effect on the operation characteristics of the electronic circuit material such as a TFT element. An object is to provide a method for forming a polymer film that can be formed. It is still another object of the present invention to provide a method for forming a polymer film capable of stably forming a color filter film having high resolution and excellent pattern accuracy directly on a substrate provided with an electronic circuit material. The present invention
A polymer film that can improve the dispersibility of the pigment more, effectively prevent the re-dissolution phenomenon of the formed polymer film, and has excellent concentration uniformity, and can form a smoother and stronger polymer film. It is an object to provide a forming method. Also,

[0010]

Means for solving the above problems are as follows. That is, <1> a first step of bringing a conductive substrate into contact with an aqueous electrolyte solution containing an electrodeposition material; and A second step of forming an electrodeposited film, wherein the aqueous electrolyte solution contains at least one of an ammonium compound and a salt thereof. Is the way.

<2> The method for forming a polymer film according to <1>, wherein the ammonium compound is an ammonium or organic ammonium compound. <3> The method for forming a polymer film according to <2>, wherein the organic ammonium compound is a tetraalkylammonium compound.

<4> The method according to <3>, wherein the salt of the tetraalkylammonium compound is a tetraalkylammonium hydroxide. <5> The above-mentioned <3, wherein the alkyl group of the tetraalkylammonium compound or a salt thereof is a methyl group or an ethyl group.
> Or <4>.

<6> The above-mentioned <1>, wherein the aqueous electrolyte further contains a coloring material, and a colored electrodeposition film is formed in the second step.
> The method for forming a polymer film according to any one of <5>.

<7> The first step is to form a substrate in which at least a light-transmitting conductive film and a light-transmitting optical semiconductor thin film having a photovoltaic function are laminated in this order on a light-transmitting substrate. A step of contacting the optical semiconductor thin film with an aqueous electrolytic solution containing an electrodeposition material containing a colorant; and a second step of irradiating the substrate with light in an aqueous electrolytic solution, and irradiating the optical semiconductor thin film with light. The method for forming a polymer film according to <6>, wherein the photoelectromotive force is selectively generated in the portion, and the electrodeposition material is electrochemically deposited to form a colored electrodeposition film. <8> The substrate according to the above <7, further comprising an electronic circuit material.
> The method for forming a polymer film according to item (1).

<9> In a first step, at least the light of a substrate comprising a light-transmitting substrate and at least a light-transmitting conductive film and an electronic circuit material bonded to the light-transmitting conductive film is provided. A step of bringing the permeable conductive film into contact with an aqueous electrolyte containing an electrodeposition material containing a coloring material, and the second step is
By driving the electronic circuit material of the substrate in a state where the light-transmitting conductive film is brought into contact with the aqueous electrolyte, the aqueous electrolyte is electrolyzed to the light-transmitting conductive film to generate hydrogen ions. A step of applying a voltage that does not generate air bubbles that generates and substantially lowers the film-forming property to deposit an electrodeposition material on the light-transmitting conductive film to form a colored electrodeposition film. 6>.

<10> The above <7> or <8>, wherein the optical semiconductor thin film contains a titanium oxide-based compound as a main component.
2. The method for forming a polymer film according to item 1. <11> The method for forming a polymer film according to any one of <6> to <10>, wherein the coloring material is a pigment, and the number average particle diameter of the pigment is 0.2 to 200 nm.

<12> The method for forming a polymer film according to any one of <1> to <11>, wherein the electrodeposition material contains a compound having a carboxyl group. <13> The compound having a carboxyl group is a polymer having a hydrophobic domain and a hydrophilic domain, and the number of hydrophobic domains is from 30 to the total number of hydrophobic domains and hydrophilic domains.
The method for forming a polymer film according to <12>, wherein the content is 85%.

<14> The polymer is a copolymer of a hydrophobic domain having a styrene structure or a substituted styrene structure and a hydrophilic domain, and the number of hydrophobic domains is 55 to 85 of the total number of hydrophobic domains and hydrophilic domains. % <
13>. <15> The method for forming a polymer film according to <13> or <14>, wherein the polymer is a styrene-acrylic acid-acrylate copolymer.

<16> The acid value of the polymer is from 60 to 200.
The method for forming a polymer film according to any one of the above items <13> to <15>. <17> 50% or more of the number of hydrophilic domains of the polymer is
The method for forming a polymer film according to any one of <13> to <16>, wherein the polymer film can be changed from water-soluble to water-insoluble or vice versa by a change in pH. <18> The number average molecular weight of the polymer is 6,000 to 250.
The method for forming a polymer film according to any one of the items <13> to <17>, which is 00.

<19> Any one of the above items <1> to <18>, wherein the pH of the aqueous electrolyte is within ± 2.5 of the pH value at which the electrodeposition material starts to precipitate and is 8.5 or less. 2. The method for forming a polymer film according to item 1. <20> The method for forming a polymer film according to any one of <1> to <19>, wherein ammonium chloride is used as a pH adjuster for the aqueous electrolyte solution.

<21> The method for forming a polymer film according to any one of <1> to <20>, wherein the aqueous electrolyte contains a conductive material. <22> The content of the aqueous solvent in the aqueous electrolyte solution is from 65 to 96% by weight based on the total weight of the aqueous electrolyte solution.
21> The method for forming a polymer film according to any one of the above items.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The method for forming a polymer film of the present invention comprises:
As the aqueous electrolyte, an aqueous electrolyte containing at least one of an ammonium compound and a salt thereof together with the electrodeposition material,
Forming a polymer film on a substrate immersed in the aqueous electrolyte, and particularly, when the aqueous electrolyte contains a coloring material, forming a polymer film (color filter film) colored according to the hue of the coloring material. I do. Hereinafter, the method for forming a polymer film of the present invention will be described.

The method for forming a polymer film according to the present invention comprises a first step of bringing a conductive substrate into contact with an electrodeposition material and an aqueous electrolyte containing at least one of an ammonium compound and a salt thereof; A second step of electrochemically depositing an electrodeposited material by a change in hydrogen ion concentration to form an electrodeposited film, and when the aqueous electrolyte solution contains a colorant, the colorant hue. (Hereinafter referred to as “colored electrodeposition film” or “colored film”), and, if necessary, forming a black matrix (hereinafter referred to as “black matrix formation”). Step)), and other steps such as a hardening step of performing a heat treatment or the like.

<First Step> In the first step, an electrically conductive substrate is treated with an electrodeposited material together with an aqueous electrolyte containing at least one of an ammonium compound and a salt thereof (hereinafter simply referred to as “electrolyte”). Contact). —Aqueous Electrolyte— As the aqueous electrolyte, an aqueous electrolyte in which at least one of an electrodeposition material, an ammonium compound, and a salt thereof is dispersed or dissolved in an aqueous solvent is used. As described below, when a colored polymer film is formed, a coloring material can be contained, and if necessary, other components such as a conductive material and a pH adjuster may be included.

(Ammonium compound, etc.)
Compounds and salts thereof include the atomic group NH_Four ⁺(Ammoni
A) with its H substituted by a hydrocarbon group, etc.
Organic ammonium compounds, and salts thereof.
In the present invention, as the ammonium compound,
Ammonium (NH_Four ⁺), As an organic ammonium compound
R_FourN⁺Type quaternary ammonium compounds (tetraalkyl
Ammonium compound) is preferable, and especially, tetra
Methyl ammonium ((CH_Three)_FourN⁺), Tetraethyla
Nmonium ((C_TwoH_Five)_FourN⁺Is preferred. In addition,
As a salt of an ammonium compound, tetraalkyl
Preference is given to salts of monium compounds, among which tetraalkyl
Luammonium hydroxide (R_FourN-OH) is more preferable
Preferably, tetramethylammonium hydroxide ((C
H_Three) _FourNOH), tetraethylammonium hydroxy
Do ((C_TwoH_Five)_FourNOH) is most preferred.

The ammonium compound and a salt thereof may be a commercially available product or a product obtained by appropriate production. The ammonium compound and a salt thereof may be dissolved and mixed with an aqueous solvent constituting an aqueous electrolyte solution to obtain an appropriate concentration of the ammonium compound. It can be used as an aqueous solution, which can also be used as a solvent for dissolving the electrodeposition material. Further, the ammonium compound or a salt thereof may be added to the aqueous solvent after or while dissolving the electrodeposition material. Two or more ammonium compounds and salts thereof may be used in combination.

When a solvent containing at least one of the above-mentioned ammonium compounds and salts thereof is used as an aqueous solvent for dissolving and dispersing the electrodeposition material, the pH of the solvent is generally lower than that of a conventionally used inorganic alkali aqueous solution. Since it is an aqueous solution of a strong strong alkali, the electrodeposition material can be dissolved in a large amount, and the pH value of the finally prepared electrolytic solution can be lowered as compared with the case where an inorganic alkali aqueous solution is used as a solvent. . That is, the pH value of the electrolytic solution is preferably somewhat lower, and after the electrodeposition film is formed on the substrate, the re-dissolution phenomenon in the electrolytic solution can be suppressed even when the voltage application is terminated. A smooth and strong polymer film can be stably formed.

Further, since the concentration of the electrodeposition material in the electrodeposition liquid can be increased, as described later, a pigment-containing polymer film (colored film / color filter) containing a coloring material such as a pigment together with the electrodeposition material. In the case of forming (1), it also acts as a dispersant for the coloring material, and can improve the dispersibility of the pigment in the electrolyte.
A colored film (color filter) having excellent concentration uniformity can be formed.

The content of the organic alkali material is preferably from 0.1 to 30% by weight, more preferably from 1 to 10% by weight, based on the aqueous solvent (weight) used. When the content is less than 0.1% by weight, the electrodeposition voltage increases, and sometimes the electrodeposition cannot be performed at a low voltage. When the content is more than 30% by weight, the electrodeposition is performed in a large amount. May not be controlled.

Conventionally, an inorganic alkaline material containing an alkaline earth metal or an alkali metal has been used in an aqueous electrolyte for the purpose of ensuring sufficient conductivity in the electrolyte.
Inorganic alkaline material shifts the V _F to the electronic circuit material such as a TFT element, tends to adversely affect the characteristics of the operation itself. Therefore, by using an organic alkali material instead of the inorganic alkali material, the above-mentioned adverse effects can be avoided, and a substrate provided with an electronic circuit material is immersed in an electrolytic solution, and a polymer film (color) is directly formed on the substrate. Even when a filter film is formed, a polymer film having high resolution and excellent pattern accuracy can be stably formed as described later without impairing the operation characteristics of the electronic circuit material.

(Electrodeposition Material) As the electrodeposition material, at least an ionic molecule whose solubility changes in response to a change in pH of a solution, a dye for coloring an electrodeposition film into a desired color,
Pigments, containing coloring materials such as pigments, if necessary,
It contains other components. Furthermore, a conductive material may be contained to form a conductive electrodeposition material, and the conductive material may be contained, or the conductive material may not be contained, and the conductive material may be used as the coloring material. It is also possible to use a coloring material.

The coloring material itself does not necessarily have to have an electrodeposition ability. When the ionic molecules are electrodeposited, the coloring material may be taken in, aggregated and precipitated to form a colored film or the like. Further, when the coloring material itself is an ionic molecule and has an electrodeposition ability, the electrodeposition material may be composed of only the coloring material. Here, it is particularly preferable to use an electrodeposition material containing a pigment and an ionic polymer as a coloring material, since the light resistance of the formed colored film can be improved. The ionic molecule may be an anionic molecule having an anion dissociable group or a cationic molecule having a cation dissociable group.

Which ionic molecule is selected as the electrodeposition material can be determined based on the change characteristic of the solubility corresponding to the change in pH of the ionic molecule. The electrodeposition material used in the present invention depends on the pH change of the solution,
Those having the property of rapidly changing the solubility are preferred.
For example, it is preferable that the solution changes its state (dissolved state → precipitated or precipitated → dissolved state) in response to a pH change of ± 2.0 of the solution, more preferably, in response to a pH change of ± 1.0. If ionic molecules having such solubility characteristics are used as an electrodeposition material, an electrodeposition film can be produced more quickly, and an electrodeposition film having excellent water resistance due to strong cohesion can be produced. Further, the ionic molecules used as the electrodeposition material preferably exhibit hysteresis in a state change (dissolution state → change in precipitation and change in precipitation → dissolution state) corresponding to a change in pH. That is, the change to the precipitation state corresponding to the decrease or increase of the pH is steep, and the change to the dissolved state corresponding to the increase or decrease of the pH is slow, so that the stability of the colored film is improved, which is preferable. .

Examples of the ionic molecule include an anionic polymer compound having a carboxyl group or the like as an anionic dissociating group; and a cationic polymer compound having an amino group or imino group as a cationic dissociating group. And the like. In the present invention, the ionic molecule used as the electrodeposition material is preferably a compound having a carboxy group, and the compound having a carboxyl group is preferably a polymer having a hydrophobic domain and a hydrophilic domain. Among the above polymers, a hydrophilic monomer having an ionic dissociating group (hydrophilic domain) and a hydrophobic monomer (hydrophobic domain)
Are preferred, among which block copolymers,
A random copolymer, a graft copolymer, or a mixture of a block copolymer and a graft copolymer or a random copolymer is more preferable. Further, in the case where a substrate having an active element which is bonded to a light-transmitting conductive film is used as the substrate and a coloring film is formed by using a driving voltage for driving the active element, dispersion of the coloring material is required. From the viewpoint of improving the properties, a block copolymer or a mixture of a block copolymer and a graft copolymer is most preferred.

When the hydrophobic monomer is represented by A and the hydrophilic monomer is represented by B in the point that the dispersibility of the coloring material is good, the block portion composed of the hydrophobic monomer A is The diblock copolymer represented by AAA-BBB and the triblock copolymer represented by BBB-AAA-BBB are particularly preferred. As the graft copolymer, BBBB is added to the polymer main chain represented by AAAAAAA.
A graft copolymer in which a plurality of side chains represented by BB are bonded is particularly preferred.

In this method, a pigment is mainly used as a coloring material. At the same time as the hydrophobic block portion made of A acts as an adsorbing group for the surface of the pigment exhibiting hydrophobicity, the polymer chains are appropriately entangled on the surface of the pigment. It is considered that aggregation of the adjacent pigments can be prevented by covering with a polymer having an appropriate thickness. At this time, B
The hydrophilic block portion consisting of has an affinity for water as a solvent,
It acts to assist the dispersion stability of the pigment in the aqueous electrolyte. Therefore, the water-insoluble pigments are kept in a state of being stably dispersed without aggregating with each other.

Examples of the hydrophilic monomer having an anionic dissociating group as a hydrophilic domain include, for example, methacrylic acid, acrylic acid, hydroxyethyl methacrylate, acrylamide, maleic anhydride, trimellitic anhydride, phthalic anhydride, hemimeritic Examples include monomers having a carboxyl group such as acid, succinic acid, adipic acid, propiolic acid, propionic acid, fumaric acid, itaconic acid and crotonic acid, and derivatives thereof. Above all, methacrylic acid, acrylic acid, and derivatives thereof are preferable because ionic polymers using these as monomers have a sharp change in state due to a change in pH and a high hydrophilicity to an aqueous liquid.

Examples of the monomer having a cationic dissociating group include primary amine, secondary amine, tertiary amine, and
Monomers having an amino group or an imino group, such as a secondary amine, oxazoline, alkylamine, alkylimine, polyamine, and polyimine. Further, the cationic polymer having a cationic dissociating group may be a polymer having a cationic dissociating group such as an amino group or an imino group introduced into the polymer. The hydrophilic monomer has 30 in its molecular structure.
Those containing an ion dissociable group in a proportion of about 75% by weight are preferred. Further, two or more hydrophilic monomers may be used in combination.

As the hydrophobic monomer (hydrophobic domain), a polymer material having an aromatic group such as an alkyl group, a phenyl group or a substituted phenyl group, a heterocyclic group, or a substituted or unsubstituted long-chain hydrocarbon group is preferred. A polymer material having an aromatic group containing an alkyl group is more preferable, and a polymer material having a styrene structure or a substituted styrene structure as a hydrophobic domain is most preferable. For example, ethylene, olefins such as butadiene, styrene, α-methylstyrene, α
-Ethyl styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate,
Lauryl methacrylate and the like, and derivatives thereof, phenylene derivatives, naphthalene derivatives and the like can be mentioned. Among them, styrene, α-methylstyrene and derivatives thereof are preferable in that they have high hydrophobicity and good electrodeposition deposition efficiency and high controllability at the time of copolymerization with a hydrophilic monomer. In addition, you may use a hydrophobic monomer in combination of 2 or more types.

Of the above, a copolymer of a hydrophilic monomer having an ionic dissociating group (hydrophilic domain) and a hydrophobic monomer (hydrophobic domain) is particularly preferably a styrene-acrylic acid-acrylate copolymer. .

The ionic polymer needs to have an appropriate hydrophilicity from the viewpoint of the liquid stability of the electrolytic solution. On the other hand, from the viewpoint of the film strength and the water resistance of the electrodeposited film, the ionic polymer needs to have an appropriate hydrophilicity. ,
It is necessary to have appropriate hydrophobicity. The balance between hydrophobicity and hydrophilicity required for an ionic polymer used as an electrodeposition material can be represented by, for example, the number of hydrophobic domains and the number of hydrophilic domains of the monomer unit as described below. That is, when the ionic polymer is a copolymer of a hydrophobic monomer and a hydrophilic monomer, the number of hydrophobic domains with respect to the sum of the number of hydrophobic domains and the number of hydrophilic domains in the monomer unit is low potential. From the viewpoint that a strong polymer film can be formed, 30 to 85% is preferable, and 60 to 80% is more preferable. In particular, in the case of a copolymer composed of a hydrophobic domain having a styrene structure or a substituted styrene structure and a hydrophilic domain such as acrylic acid or a derivative thereof, the number of the hydrophobic domains is 55 to 85%. Is preferred. If the ratio of the number of the hydrophobic domains is less than 30%, a redissolved phenomenon of the deposited film is likely to occur, and the water resistance and the film strength of the electrodeposited film may be insufficient, and may exceed 85%. In addition, the affinity of the ionic polymer for the aqueous solvent is reduced, so that an appropriate amount cannot be dissolved, or precipitation occurs, or the viscosity of the electrolytic solution becomes too high to form a uniform electrodeposition film. is there. On the other hand, when the number of hydrophobic domains is in the above range, the affinity with the aqueous solvent is high, the liquidity of the electrolytic solution is stabilized, and the electrodeposition efficiency is high.

On the other hand, as the hydrophilic group, at least 50% of the number of the hydrophilic groups is a hydrophilic group which can be changed from water-soluble to water-insoluble or, conversely, reversibly changed by a change in pH. preferable. If the number of the hydrophilic groups is less than 50%, the solubility in water may be too low to be insoluble in water.

The balance between hydrophobicity and hydrophilicity of an ionic polymer can be indicated by an acid value when an anionic polymer is used. The acid value of the anionic polymer is preferably from 60 to 200, and more preferably from 70 to
130 is particularly preferred. If the acid value of the anionic polymer is less than 60, the affinity for the aqueous solvent is low, the anionic polymer is precipitated, and the viscosity of the electrolyte solution is too high, so that a uniform electrodeposition film is formed. May not be formed, and if it exceeds 200, the water resistance of the formed electrodeposition film may be reduced, and the electrodeposition efficiency may be reduced.

The number average molecular weight of the ionic molecule is 6.0 × 10 6 from the viewpoint of the film properties of the electrodeposited film.
^{3 to} 2.5 × 10 ⁴ is preferred, and 9.0 × 10 ^{3 to} 2.0
× 10 ⁴ is more preferred. The number average molecular weight is 6.0
If it is less than × 10 ³ , the film becomes non-uniform and the water resistance is reduced. As a result, cracks are generated in the electrodeposited film or the electrodeposited film is powdered to obtain an electrodeposited film having high robustness. If it exceeds 2.5 × 10 ⁴ , the affinity with the aqueous solvent may be reduced, and precipitation may occur, or the viscosity of the electrolytic solution may be too high, resulting in an uneven electrodeposition film.

When the ionic polymer has a glass transition point of 100 ° C. or less, a flow starting point of 180 ° C. or less, and a decomposition point of 150 ° C. or more, preferably 220 ° C. or more, the ionic polymer may have an on-substrate. This is preferable because the film properties of the electrodeposited film made of an ionic polymer formed as described above are improved, and the electrodeposited film formed later is less likely to be deteriorated by a film formed later.

(Coloring Material) As described later, when a colored electrodeposition film is formed, a coloring material is contained in an aqueous electrolyte solution. Examples of the coloring material include coloring materials such as dyes and pigments. Pigments are preferred from the viewpoints of light resistance and the ability to stably form a film having a uniform thickness. Examples of the pigment include general-purpose known pigments, such as azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, and anthraquinone pigments. As the number average particle diameter of the pigment,
It is preferably from 0.2 to 200 nm, more preferably from 40 to 60 nm. When the number average particle diameter is less than 0.2 nm, the cost during production is increased, and stable quality may not be obtained. May occur.

When the electrodeposition material contains an ionic coloring material, examples of the ionic coloring material include triphenylmethanephthalide, phenosazine, phenothiazine, fluorescein, indolylphthalide, and the like. Spiropyran, azaphthalide, diphenylmethane, chromenopyrazole, leuco auramine, azomethine, rhodamine lactal, naphtholactam, triazene,
Examples include triazole azo, thiazole azo, azo, oxazine, thiazine, benzothiazole azo, and quinone imine dyes, and hydrophilic dyes having a carboxyl group, an amino group, or an imino group.

However, it is particularly preferable to use a pigment from the viewpoint that a film having a uniform thickness can be stably formed. Examples of the pigment include general-purpose known pigments, such as azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, and anthraquinone pigments.

The ammonium compound and its salt not only can increase the concentration of the electrodeposition material in the electrolytic solution, but also function as a dispersant for the coloring material itself, and improve the dispersibility of the pigment in the electrolytic solution. Can be improved. Therefore, a colored film (color filter film) having more excellent concentration uniformity can be formed.

(Conductive Material) It is also possible to form a conductive polymer film. In order to further improve the conductivity, it is preferable to include a conductive material in the aqueous electrolyte solution. Specifically, a conductive electrodeposition material containing a conductive material or a conductive coloring material can be used. Examples of the conductive material include a light-transmitting conductive material, a light-transmitting conductive polymer compound, a salt, and a conductive coloring material.

As the light-transmitting conductive material, IT
Examples thereof include transparent conductive materials such as O and SnO ₂ , and mixtures thereof. Examples of the conductive coloring material include carbon black and the like in addition to the ionic coloring material.

Examples of the salt include salts that do not affect the electrodeposition properties, such as inorganic salts such as NaCl, KCl, and NH ₄ Cl, and organic salts such as tetraethylammonium chloride and tetraethylammonium perchlorate. There are various combinations of salt types, and the cations include alkali metal ions, ammonium ions, and quaternary salts.
Examples of the anion include a halogen ion, a sulfate ion, a perchlorate ion, a nitrate ion, a sulfonate ion, BF ⁴⁻ , and PF ⁴⁻ . Among them, ions that are less susceptible to oxidation and reduction are preferred in terms of imparting conductivity, and further, in terms of solubility in water, halogen ions, nitrate ions, sulfate ions,
Ammonium salts and quaternary ammonium salts of sulfonic acid ions are more preferred. On the other hand, a thin film transistor (TF
From the viewpoint of not impairing the effect of the present invention of not adversely affecting T), it is better to avoid alkali metals.

The aqueous electrolyte solution is used by dissolving or dispersing the electrodeposition material in an aqueous solvent. The aqueous solvent is mainly composed of water and, if desired, contains alcohol or the like as long as the effects of the present invention are not impaired. It refers to a solvent to which other solvents having an affinity for water or various salts and additives are added. In the aqueous electrolyte solution, the content of the aqueous solvent (component weight ratio)
It is preferably 65 to 96% by weight based on the total weight of the aqueous electrolyte.

(Substrate) As the substrate, any conductive material can be used. In addition to the same substrates as described later, when it is not necessary to be light-transmitting, for example, a metal plate or a conductive material may be used. An opaque plastic material or the like can be appropriately selected depending on the purpose.

-Second Step- In the second step, an electrodeposition material is electrochemically deposited on a substrate having at least a conductive film on a base pair by changing a hydrogen ion concentration to form an electrodeposition film. Form. This step is based on a film forming technique using an electrodeposition technique, and focuses on, among water-soluble molecules, molecules whose solubility in water can be greatly changed in an oxidized state, a neutral state, and a reduced state. This method utilizes the principle of enabling the transfer between the above states by directly electrochemically redoxing the water-soluble molecules or by appropriately changing the pH of the aqueous solution in which the water-soluble molecules are dissolved.

That is, a voltage is applied to the substrate on which the polymer film is to be formed, and the pH is caused by a change in the pH of the liquid generated near the surface of the substrate due to the electrolysis of water in the electrolytic solution. For example, there are a method of directly energizing the substrate, a method of forming an optical semiconductor thin film on the substrate, irradiating the film with light, and using a photoelectromotive force generated only in the light-irradiated portion. The formed electrodeposition film can be re-eluted into the aqueous solution by applying a reverse voltage or immersing it in an aqueous solution having a pH of 10 to 12.

Here, by using an aqueous electrolyte containing an electrodeposition material containing a coloring material, a colored polymer film having a desired image pattern can be formed. By repeating this process using each of the red, green, and blue aqueous electrolytes, a polymer film of a plurality of colors can be formed. Therefore, unlike the conventional electrodeposition method, a transparent conductive film that has been patterned in advance is unnecessary, and an arbitrary image pattern can be formed at a high resolution by a simple and low-cost method without going through a photolithography process. it can. When a conductive material is contained in the electrolytic solution, a conductive electrodeposited material is deposited on the substrate, and a conductive polymer film can be formed.

As a method for forming a polymer film of the present invention, an aqueous electrolyte containing at least one of an ammonium compound and a salt thereof is used, and a substrate on which a polymer film is to be formed is brought into contact with the aqueous electrolyte. Any method may be used as long as a polymer film is formed by electrochemically depositing an electrodeposition material by a photoelectrodeposition method or an electrodeposition method. Among them, as a preferred embodiment,
For example, the formation method shown in the following first embodiment or second embodiment can be used.

-First Aspect- In this aspect, in the first step, at least a light-transmitting conductive film and a light-transmitting optical semiconductor thin film having a photovoltaic function are formed on a light-transmitting substrate. A step of contacting the optical semiconductor thin film of the substrate obtained by laminating in this order with an electrolytic solution containing at least one of an ammonium compound and a salt thereof together with an electrodeposition material containing a coloring material (hereinafter, may be referred to as a “contact step”) ), And as the second step, irradiating the optical semiconductor thin film on the substrate with light in an electrolytic solution to selectively generate a photoelectromotive force in a light-irradiated portion of the optical semiconductor thin film, Forming a colored electrodeposition film by selectively depositing the electrodeposition material (hereinafter referred to as “colored electrodeposition film forming step”).
There is that. ), And if necessary, a black matrix forming step, a hardening step and the like.

[Contact Step] In the contact step, at least the above-mentioned step is performed for a substrate in which a light-transmitting conductive film and a light-transmitting optical semiconductor thin film having a photovoltaic function are laminated in this order on a light-transmitting substrate. This is a step of bringing the optical semiconductor thin film into contact with an electrolytic solution containing an electrodeposition material containing the above-described coloring material.

When the optical semiconductor thin film of the substrate is brought into contact with the electrolytic solution, any positional relationship with the electrolytic solution can be appropriately selected. For example, the entire substrate is immersed in the electrolytic solution and arranged. Alternatively, it may be arranged such that only a part of the substrate, for example, only the optical semiconductor thin film forming the colored electrodeposition film is in contact with the substrate. In this aspect, since the coloring material is contained in the electrolytic solution, at least the portion where the colored electrodeposition film is to be formed is arranged so as to be in contact with the electrolytic solution, and the surface on the back side of the portion where the colored electrodeposition film is to be formed. It is preferable that the (the surface of the substrate on which the optical semiconductor thin film is not provided) be present outside the electrodeposition liquid.

When an image pattern is formed by irradiating light onto a substrate on which a conductive film and an optical semiconductor thin film are formed, generally, a photomask is brought into close contact with the surface of the optical semiconductor thin film of the substrate, and the photomask is exposed from above the photomask. The parallel light may be irradiated by the light source. However, as described above, the electrodeposition liquid contains a component capable of absorbing light, such as a coloring material, so that even if the photomask is brought into close contact with the electrolytic solution and irradiated with light, No image pattern can be obtained. Therefore, a photomask is arranged on the surface (back surface) of the substrate on which the optical semiconductor thin film on which the colored electrodeposition film is to be formed is not provided,
It is preferable that the light is irradiated from above the photomask on the back surface so that the irradiation light does not pass through the electrolytic solution.

Here, when light is incident on the optical semiconductor thin film on which a colored electrodeposition film is to be formed, the incident light travels through the substrate and the conductive film in the thickness direction of the substrate, so that the light coming into contact with the electrolytic solution is exposed. Before reaching the surface of the semiconductor thin film, the light may be diffused or the resolution may be reduced due to the influence of diffraction. Therefore, at least the second imaging optical member or the mirror reflecting optical member and at least the conductive material from the substrate surface on which the optical semiconductor thin film (exposure surface) on which the black matrix and the colored electrodeposition film are to be formed are not provided. Using a photomask for patterning a substrate in which a film and an optical semiconductor thin film are laminated in this order, a first imaging optical member, and a light source, using an exposure apparatus arranged in this order,
An image is formed on the photomask from the light source through the first imaging optical member, and the light in the form of an image pattern coming out through the photomask is further imaged on the exposure surface through the second imaging optical member. Embodiments are more preferred.

[Colored Electrodeposition Film Forming Step] In the colored electrodeposition film formation step, the optical semiconductor thin film on the substrate is irradiated with light in a state of being in contact with a desired electrolytic solution, and the light irradiating part of the optical semiconductor thin film is irradiated onto the light irradiated part of the optical semiconductor thin film. This is a step of selectively generating photoelectromotive force and electrochemically depositing the electrodeposition material to form a colored electrodeposition film. As described above, the colored electrodeposition film forming step in this embodiment is based on the film forming technique using the electrodeposition technique, and enables the water-soluble molecules to move between the oxidized, neutral and reduced states. It is based on the principle.

However, in order to form a colored electrodeposition film, it is necessary to apply a voltage higher than a certain threshold value, and even if a current simply flows, the electrodeposition film is not necessarily formed. Therefore, by applying a bias voltage,
Even if the voltage level input from the outside is low, a colored electrodeposition film can be formed, and a desired colored electrodeposition film can be formed by controlling the input voltage level to be used. Here, if a semiconductor material is used for the substrate on which the colored electrodeposition film is to be formed, and if the electrode is used as an electrode, light is used for an input signal, and furthermore, the irradiation of this light is controlled to control the colored electrodeposition film at a desired position. Can be formed, and an arbitrary image pattern can be formed.

Specifically, as described above, specifically, as described above, a solution (hereinafter, referred to as an “electrolytic solution”) in which an electrodeposition material containing a pigment or a dye whose solubility greatly changes due to a change in liquid properties is dissolved and dispersed. Is prepared, and an organic or inorganic semiconductor material is brought into contact with or immersed as an electrode in the electrolytic solution in the bath, and the semiconductor material is irradiated with light so as to correspond to a desired image pattern. By irradiating on the upper side, the electrodeposition material in the electrolytic solution is deposited on the semiconductor material, and a monochromatic color filter having a color filter layer of a desired image pattern can be formed. By repeating this using each of the red, green and blue electrolytes,
A multi-color filter can be formed. Therefore, as described above, an arbitrary image pattern can be formed smoothly and with high resolution without a photolithography step at a low cost. Further, when a conductive electrodeposition material is used as the electrodeposition material in the electrolytic solution, a conductive color filter formed of a conductive color filter film can be formed.

In the case of anodic electrodeposition, the pH value of the aqueous electrolyte solution before light irradiation is the pH at which the state of the electrodeposition material used changes.
In the case of cathodic electrodeposition, the pH is preferably set within a range of -2.5 from the pH value at which a change in the state of the electrodeposition material used occurs, and the pH is preferably 8.5 or less. preferable. That is, while the electrodeposited material shows sufficient solubility in the aqueous solvent used for the electrolytic solution, a change in the pH of the electrolytic solution from the dissolved or dispersed state to the formation of a supernatant and the precipitation causes the pH to fall within the range of 3.0. It is preferably within the range. More preferably, it is within 1.5.

If the pH value of the aqueous electrolyte is set in such a range, the dissolution of the electrodeposition material in the aqueous solvent becomes saturated before the colored electrodeposition film is formed. As a result, once the colored electrodeposition film is formed, it is difficult to redissolve in the aqueous electrolyte after the film is formed, and a stable and highly transparent colored electrodeposition film can be formed. On the other hand, at the time of forming the colored electrodeposition film, when the electrodeposition material is in an unsaturated state, that is, when the pH value of the electrolytic solution is not in the above range, the deposition rate is reduced, or Is formed, the film may be redissolved as soon as the supply of current or the like is stopped. In order to adjust the pH value of the electrolytic solution, an acidic or alkaline substance which does not affect the electrodeposition characteristics is added, and the bias voltage is adjusted to 5%.
It is preferable to form the colored film by lowering the voltage to V or less.
It is more preferable to form the colored film by lowering the voltage to V or less.

Further, from the viewpoint of forming a black matrix and a colored electrodeposition film having a sharp edge portion and a high sharpness, the temperature of the electrolytic solution used at the time of electrodeposition is maintained at a constant temperature, and at a constant electrodeposition speed. It is preferable to form a black matrix and a colored electrodeposition film.

In the electrolytic solution, for the purpose of increasing the electrodeposition speed,
In addition to the electrodeposition material, an ion dissociating salt which does not affect the electrodeposition properties may be added, and the addition of the salt increases the conductivity of the solution. The conductivity in the aqueous liquid is correlated with the electrodeposition speed (in other words, the amount of electrodeposition). The higher the conductivity, the thicker the electrodeposition film deposited in a certain period of time, and the higher the conductivity. Saturation is reached at about 100 mS / cm ² (corresponding to 10 Ω · cm). Therefore, ions that do not affect the formation of a colored electrodeposition film in the electrolyte, for example, Na ⁺ , NH ₄ ⁺ , C
_{^{l -, PO 4 -, SO}} 4 - be added to the like, it is possible to control the electrodeposition rate. Among them, as the salt to be added,
Ammonium chloride is preferred. To adjust the volume resistivity of the electrolyte solution by the addition of the salt, the said volume resistivity is preferably ^{10 0 ~10 5 [Ω · cm} ].

Next, a description will be given of a change in pH of the electrolytic solution occurring near the substrate and a formation mechanism of the colored electrodeposition film accompanying the change. Generally, when donating soaked current or voltage a platinum electrode in an aqueous solution, OH in the aqueous solution in the anode vicinity ^- ions become O ₂ is consumed, pH is lowered by increasing the hydrogen ions. This is because the hole (p) and OH near the anode
^- because the less reactive the lead and the ions occurs. 2OH ⁻ + 2p ⁺ → 1/2 (O ₂ ) + H ₂ O However, in order for this reaction to occur, the potential of the substrate needs to exceed a certain value (threshold potential). The reaction proceeds only after exceeding the threshold potential, and the pH in the aqueous solution changes (the pH decreases near the anode and increases near the cathode). In the case of forming a colored electrodeposition film in the present invention, photoelectromotive force is generated in the optical semiconductor by light irradiation, only the light irradiated portion is set to a potential exceeding the threshold potential, and only the electrolyte near the light irradiated portion of the substrate is applied. The above reaction proceeds. As a result of the progress of the reaction, p
H changes, and the solubility of the electrodeposition material changes correspondingly, and a colored electrodeposition film is formed only on the light irradiation part.

As described above, the electrochemi
Attempts to elicit a response have been investigated in various ways.
Was. For example, A. Fujishima, K .; Hand
a, Nature vol. 238, p37, (197
2) The n-type optical semiconductor TiO _TwoIrradiate the light
Of electrolysis of water by photovoltaic power
ing. Also, as an example of image formation using photovoltaic
Is H. See Yoneyama, et al. Elec
trochem. Soc. , P2414 (1985)
Irradiate light onto the Si substrate, and the generated photovoltaic
Pyrole is electrolytically polymerized and is defined by doping and undoping.
An example of performing image formation has been reported. Also we are also conductive
Dyes for doping and undoping of conductive polymers
A patent application is pending for a method of forming an image by using. But photovoltaic
When conducting image formation with conductive polymer using electric power
In such a case, there are limitations on the color developing materials that can be used. As a result,
It was difficult to form a colored image.

Even in a system in which no conductive polymer is present,
Although it is possible to form a colored electrodeposition film, the voltage required for forming the colored electrodeposition film is higher than that when a conductive polymer is present. For example, in JP-A-5-119209, "Color filter manufacturing method and electrodeposited substrate for manufacturing color filter", and in JP-A-5-157905, "Color filter manufacturing method", an optical semiconductor thin film is irradiated with light. There is disclosed a technique for forming a colored electrodeposition film using photoconductivity developed in the light irradiation part, but the applied voltage is from 20 V to 80 V, and the electrodeposition material is a redox reaction of a polymer. I use. On the other hand, the photoelectromotive force of the optical semiconductor thin film is less than 1 V (for example, about 0.6 V for Si),
Photovoltaic power alone is not enough to form an image. Although it is conceivable to raise the potential in advance by applying a current or a voltage, if a voltage exceeding a certain voltage (a voltage corresponding to a band gap of an optical semiconductor to be used) is applied (for example, a voltage exceeding 5 V with Si). ), The Schottky barrier between the semiconductor and the electrodeposition liquid is broken, so that an image cannot be formed. In the present invention, as described above, a colored electrodeposition film is formed by utilizing a change in solubility of an electrodeposition material corresponding to a change in pH in an electrodeposition solution without using a redox reaction of a polymer or the like for electrodeposition. Therefore, electrodeposition can be performed within a range that does not destroy the Schottky barrier.

In the present invention, a voltage may be applied to the substrate (light-transmitting conductive film in the substrate) in advance. Here, in the case of a configuration of a tripolar arrangement generally used in the electrochemical field, a bias voltage is applied so that a potential difference between an anode and a cathode or a reference electrode is 4 V or less, preferably 2 V or less. It is preferable to form an electrodeposition film or a black matrix described later. The bias voltage applied at this time compensates for the potential generated in the substrate by the photovoltaic force generated by the optical semiconductor thin film, and the magnitude thereof is set so that the potential of the substrate reaches the threshold potential. Further, the applied bias voltage is set to a magnitude not exceeding the Schottky barrier. If the voltage applied to the substrate in advance is too high, the Schottky barrier is broken, current flows even in the area not irradiated with light, and an electrodeposition film is formed on the entire area of the optical semiconductor substrate. Can no longer be controlled. For example, the photovoltaic power of TiO ₂ is about 0.6
V, so if it is an electrodeposition material that is electrodeposited at 2.0 V,
When light irradiation is performed while applying a bias voltage of 1.5 V, the potential of the light irradiation portion of the substrate (optical semiconductor film) becomes 0.6 V + 1.5.
V = 2.1 V, which exceeds the threshold potential required for electrodeposition, and a colored electrodeposition film is formed only on the light irradiation part. On the other hand, when a bias voltage of 2.5 V or more is applied to this substrate, the Schottky barrier is broken.

Next, the combination of the optical semiconductor and the electrodeposition material will be described. In the present invention, a photovoltaic voltage is formed by using a Schottky barrier generated at an interface in contact with an optical semiconductor or a pn.
A barrier of a junction or a pin junction is used. FIG. 1 schematically shows a Schottky barrier generated at an interface between an n-type optical semiconductor and an electrodeposition liquid, and FIG. 2 schematically shows an energy band of a pin junction. For example, when an n-type optical semiconductor is used, when the n-type optical semiconductor side is made negative, current flows because the current flows in the forward direction, but conversely, when the n-type optical semiconductor side is made positive. In the method, a Schottky junction between the n-type optical semiconductor and the electrolyte forms a barrier, and no current flows. However, even in a state where the current does not flow with the n-type optical semiconductor side being positive, when light is irradiated, electron-hole pairs are generated from the n-type optical semiconductor thin film, the holes move to the solution side, and the current flows. In this case, the material to be electrodeposited must be an anionic molecule because the n-type optical semiconductor is brought to a positive potential. Therefore, a combination of an n-type optical semiconductor and an anionic molecule is formed, and conversely, a cation is electrodeposited in a p-type optical semiconductor.
In particular, it is preferable to use a colored electrodeposition material containing a cationic molecule having an anionic molecule having a carboxyl group when using an n-type optical semiconductor and an amino group or an imino group when using a p-type semiconductor. .

To apply a current or voltage to the conductive film,
A current path for supplying a current or a voltage may be provided at a side edge of the conductive film or the like. A potentiostat or the like can be used to supply current or voltage.

After the step of forming a colored electrodeposition film of each color or the step of forming a black matrix described later, the substrate may be subjected to liquid cleaning in order to remove the electrolytic solution adhered to the substrate and used in each step. . As a cleaning liquid to be used, a transparent and highly safe inert liquid is preferable. Further, it is more preferable to use a cleaning liquid that promotes solidification of the colored electrodeposition film because the film strength of the colored electrodeposition film is improved. As such a washing liquid, an aqueous liquid which is adjusted to a pH at which the electrodeposition material contained therein is more likely to precipitate than the pH value at which the electrolytic solution starts to be deposited is preferable. When the substrate on which the colored electrodeposition film is formed is washed with such a pH adjusting solution, the electrolytic solution and the like used in the previous step adhered to the substrate can be removed, and the film strength of the colored electrodeposition film can be improved. Can be. By such washing, for example, when an electrodeposition material having an anionic dissociation group such as carboxyl group is used, the pH value of the washing solution is lower than the pH value at the start of the deposition of the electrodeposition material, In the case of an electrodeposition material having a cationic dissociating group, the pH of the washing solution
By setting the value to be higher than the pH value at the start of the deposition of the electrodeposited material, the robustness of the electrodeposited film is improved, and as a result, a color filter with high resolution can be produced.

[Hardening Step] In the method for forming a polymer film according to the present invention, from the viewpoint of improving the film strength and solvent resistance of the formed film, the colored electrodeposition film forming step and the black matrix forming step described later are performed. After the above, a hardening step of irradiating the formed polymer film with light, heating or the like may be provided. in this case,
The aqueous electrodeposition solution may contain a radical generator or an acid generator, and among them, a heat-reactive one is preferred in that a radical or an acid can be uniformly generated in the film.

This hardening step may be provided sequentially after forming the colored electrodeposition films of each color, may be provided after forming the three color RGB electrodeposited films, or may be provided after the black matrix is provided. They may be provided collectively. However, from the viewpoint of sufficiently improving the film properties of each film, it is preferable to sequentially perform the hardening step after forming the colored electrodeposition film of each color. When the black matrix is provided first by the photoelectric deposition method, the black matrix may be provided only after the black matrix is formed.

Examples of the heating method for heating the film include a method in which the film is heated in an oven or a vacuum heater adjusted to a desired temperature and a method in which a heating gas is sprayed on the surface. The heating temperature is preferably from 50 to 250 ° C, more preferably from 90 to 200 ° C.

-Substrate- The substrate that can be used in this embodiment is not particularly limited as long as it has the cross-sectional structure shown in FIG. 3 on the whole or a part of the substrate, and further has an electronic circuit material. You may. That is, the substrate is formed by sequentially laminating at least a light-transmitting conductive film 32 and an optical semiconductor thin film 33 having a photovoltaic function on a light-transmitting base 31, and the laminated portion is When formed on the whole or a part of the substrate 31 and formed on the part thereof, the conductive film 3 is formed in a state of directly contacting the surface of another region of the substrate 31 excluding the part, or
2, or an electronic circuit material may be provided via the conductive film 32 and the optical semiconductor thin film 33. In particular,
For example, the substrate may be configured as shown in FIGS. 4- (a) to (c). Here, as the electronic circuit material,
The same thing as the thing in the below-mentioned 2nd aspect is mentioned.

(Substrate) As the substrate, various light-transmitting materials can be used. For example, glass, plastic, and the like are preferable.

(Conductive Film) The conductive film can be widely used as long as it has conductivity and is light-transmitting. For example, metal oxides such as ITO (indium-tin oxide) and tin dioxide are exemplified. Alternatively, a conductive carbon material, a conductive ceramic material, or the like can be used. The conductive film is, for example, an evaporation method, a sputtering method,
It can be formed on a support by a conventionally known method such as a CVD method.

(Optical Semiconductor Thin Film) Any optical semiconductor thin film can be used as long as it generates a photoelectromotive force by light irradiation. Although the optical semiconductor has an optical hysteresis effect that retains the effect of light irradiation for a certain period of time, the optical semiconductor used in the present invention preferably has a weak optical hysteresis effect. However, even if the optical hysteresis effect is strong, the optical hysteresis effect tends to be reduced if the optical semiconductor thin film is thinned, so that it can be used. The optical semiconductor includes an n-type optical semiconductor and a p-type optical semiconductor, and any optical semiconductor can be used in the present invention. Further, an optical semiconductor thin film having a pn junction in which an n-type optical semiconductor thin film and a p-type optical semiconductor thin film are laminated, or n
An optical semiconductor thin film having a pin junction in which a type optical semiconductor thin film, an i-type optical semiconductor thin film, and an n-type optical semiconductor thin film are laminated,
The use of an optical semiconductor thin film having a laminated structure is preferable because a high-output photocurrent can be reliably obtained and the contrast of an image can be further increased.

The optical semiconductor thin film used in the present invention may be made of an inorganic optical semiconductor or an organic optical semiconductor. As the inorganic optical semiconductor, titanium oxide, silicon carbide, zinc oxide, lead oxide, nickel oxide, tin oxide, molybdenum oxide, SiGaN, a-
C, BN, ZnSe, diamond, GaAs-based compounds, CuS, Zn ₃ P ₂ , polysilicon and the like.
Examples of the organic optical semiconductor include phthalocyanine pigments, perylene pigments, azo pigments, polyvinyl carbazole, polyacetylene, and the like. These are individually desired to be of high purity or single crystal type, but may be composed of a mixture thereof, or may be a laminate of a plurality of optical semiconductor thin films composed of each material. . In particular,
Compound optical semiconductor thin films containing titanium oxide are preferred.

Among them, metal oxides such as TiO ₂ and ZnO have excellent stability during electrodeposition and excellent light irradiation efficiency.
Further, TiO ₂ is prepared by a sol-gel method, a sputtering method,
Recent studies have shown that a good n-type optical semiconductor thin film can be obtained by forming a film by various methods such as an electron beam evaporation method. In order to increase the conversion efficiency of the photocurrent, a reduction treatment is effective. Usually, heating is performed at about 300 ° C. in hydrogen gas. For example, it can be achieved by heating at about 300 ° C. for 10 minutes while using a 3% hydrogen mixed nitrogen gas at a flow rate of 1 L per minute.

The optical semiconductor thin film can be formed on a conductive film by a conventionally known sol-gel method, sputtering method, electron beam evaporation method, ion coating method, glow discharge deposition method, or the like. The thickness of the optical semiconductor thin film is not particularly limited, but is 0.05% in that good characteristics can be obtained.
~ 3.0 µm is preferred. When the film thickness is less than 0.05 μm, the generated photovoltaic force is too weak, which may cause a problem in pattern formation. When the film thickness is more than 3.0 μm, charges generated by light irradiation are trapped in the film, Since the light hysteresis effect is increased, pattern formability may be deteriorated.

The optical semiconductor thin film preferably has a microcrystalline or polycrystalline film quality in terms of photovoltaic power generation efficiency. Further, those made of only an optical semiconductor are preferable, and those containing no insulating material such as resin are preferable. When an insulating material such as a resin is mixed with the optical semiconductor thin film, the generation efficiency of photovoltaic power is reduced, and the light hysteresis effect is enhanced. The volume resistivity of the optical semiconductor thin film under light irradiation is 10 ^−2.
Preferably ~10 ⁸ Ω · cm, and more preferably 10 ⁰ ~10 ⁶ Ω · cm. The optical semiconductor thin film has a volume resistance of 10
^If it exceeds ⁸ Ω · cm, a high voltage is required for energization, and the generation efficiency of photovoltaic power may be significantly reduced.

An example of a method for forming a colored electrodeposition film (color filter film) according to this embodiment will be briefly described with reference to FIG. The electrodeposition bath 1 is filled with an aqueous electrodeposition solution in which an ammonium compound or a salt thereof is dissolved and dispersed together with the electrodeposition material 2 and the black pigment 3, and a counter electrode 6 is disposed in the electrodeposition bath. It is connected to a power supply not shown. In the electrodeposition bath 1, an electrodeposition substrate 4 having a cross-sectional structure similar to that shown in FIG. 4A, in which a conductive film and an optical semiconductor thin film are sequentially laminated on a base and an electronic circuit material is provided. It is arranged so as to be immersed, and is connected to a power supply via a working electrode 7 connected to the conductive film.

The electrodeposition tank 1 is configured to transmit light, and a light source is arranged outside the electrodeposition tank at a position where light can be irradiated to the electrodeposition substrate 4 in a direction indicated by an arrow in the figure. Have been.
The electrodeposition substrate 4 is irradiated with a laser beam controlled in accordance with an image signal from a light source through a photomask or in an image pattern in a state where a negative bias voltage is applied through the conductive film.

When a p-type semiconductor substrate is used as the electrodeposition substrate 4, a negative photovoltaic power is generated only in the light irradiated portion of the optical semiconductor thin film, and the total potential of the negative photovoltaic power and the negative bias voltage is reduced. When the threshold value at which the electrodeposition of the electrodeposition material in the electrolytic solution is started is exceeded, a black matrix is first formed only in the light-irradiated portion. On the other hand, when an n-type semiconductor substrate is used as the electrodeposition substrate 35, the reduction reaction of metal ions in the electrolytic solution is suppressed in the light-irradiated portion of the optical semiconductor thin film, but in a non-irradiated portion, a negative bias voltage is applied. Metal ions in the electrodeposition material of the electrolytic solution are reduced, and a black matrix is formed only in the unirradiated portion.

After the black matrix is formed on the electrodeposition substrate 4, the aqueous electrodeposition solution is mixed with any one of the electrodeposition material 2 and the RGB pigment to obtain at least one of an ammonium compound and a salt thereof. A black matrix on the electrodeposition substrate 4 is not formed by applying a positive bias voltage instead of the liquid in sequence and irradiating light through a photomask corresponding to each color or by a laser beam controlled according to an image signal. A colored electrodeposition film of each color is selectively formed on a part of the light irradiation portion, and a color filter having a desired color image pattern can be manufactured.

As described above, by using an aqueous electrolyte in which a pigment is well dispersed, a high-resolution color filter having an extremely uniform coloring concentration and film thickness and excellent pattern accuracy can be manufactured at low cost. it can.

-Second Aspect- In the second aspect, in the first step, at least a light-transmitting conductive film and a light-transmitting conductive film are bonded on a light-transmitting substrate. Providing a step of contacting at least the light-transmitting conductive film of the substrate with the active element with an electrolytic solution containing at least one of an ammonium compound and a salt thereof together with an electrodeposition material containing a coloring material, Further, in the second step, the active element on the substrate is driven in a state where the light-transmitting conductive film is in contact with the electrolytic solution, whereby the electrolytic solution is electrolyzed to the light-transmitting conductive film. To generate hydrogen ions (protons) and to apply a voltage that does not or hardly generates air bubbles that substantially lowers the film forming property, thereby depositing an electrodeposition material on the light-transmitting conductive film. To form a colored electrodeposition film A step (colored electrodeposition film forming step) is provided, and a black matrix forming step, a hardening step, and the like are provided as necessary.

[Contacting Step] The contacting step is performed at least on the substrate having a light-transmitting conductive film and an active element bonded to the light-transmitting conductive film on a light-transmitting substrate. This is a step of bringing the conductive film into contact with an electrolytic solution containing an electrodeposition material containing at least a coloring material. Here, the active element refers to a switching element provided with a source electrode, a drain electrode, a gate electrode, and a semiconductor thin film that is provided adjacent to and joined to a light-transmitting conductive film. TFT; hereinafter, sometimes simply referred to as “TFT”). As described above, when a light-transmitting conductive film (hereinafter, sometimes referred to as a “transparent conductive film”) is brought into contact with an electrolytic solution, a thin film transistor (TFT) provided over the same base and chromium (Cr) ) And aluminum (Al) source electrode, drain electrode and gate electrode are easily deteriorated by contact with water,
Since short-circuiting is likely to occur during driving, it is preferable to perform insulation treatment in advance, leaving only the transparent conductive film on which a colored electrodeposition film is to be formed. The method of the insulation treatment will be described later.

When the transparent conductive film of the substrate is brought into contact with the electrolytic solution, any positional relationship with the electrolytic solution can be appropriately selected. For example, the entire substrate is immersed in the electrolytic solution and arranged. Alternatively, it may be arranged so that only a part of the substrate, for example, a transparent conductive film forming a colored electrodeposition film is in contact with the substrate.

As an insulation treatment, a resin solution in which an ultraviolet-curable resin is dissolved in an appropriate solvent is applied, only the transparent conductive film portion is masked, and the entire surface is irradiated with an ultraviolet lamp to be cured. A method for dissolving and removing the resin solution on the transparent conductive film, after coating the surface of the negative photoresist solution with a coating device such as a spinner and pre-baking, exposing the transparent conductive film, decomposing and developing with a solvent, and not exposing A method of curing the portion by host baking, or the like can be given.
When the insulating treatment is performed as described above, a black color material may be contained in an insulating material to be used, and a black matrix may be formed by forming a black insulating film. In this case, examples of the black color material that can be used include two-color or three-color mixed pigments such as carbon black and phthalocyanine pigments. However, since the portion where the active element is arranged is light non-transmissive, it is not always necessary to form the above-described black matrix.

[Colored Electrodeposition Film Forming Step] In the colored electrodeposition film formation step of this embodiment, the active element bonded to the transparent conductive film on which the colored film is to be formed is driven.
In a transparent conductive film selected from a plurality of transparent conductive films provided on the same substrate, the electrolytic solution electrolyzes on the transparent conductive film to generate protons, and substantially reduces film formability. By applying a voltage that does not or hardly generates air bubbles, an electrodeposition material is deposited on the transparent conductive film to form a colored electrodeposition film. Therefore, in the case of full color, it is necessary to separately form red (R), green (G), and blue (B) colored films on three adjacent transparent conductive films, respectively. First, after bringing three adjacent transparent conductive films into contact with a red electrolyte in which a red pigment and a water-soluble polymer material are dispersed, a driving IC connected to each transparent conductive film is controlled. Only the thin film transistor (TFT) corresponding to the red pixel is driven, and a red film is formed only on the transparent conductive film corresponding to the TFT. The formed red film is washed with water, dried and fixed if necessary, and is preferably subjected to a water insolubilization treatment. Next, the same process is repeated using an electrolyte for blue and an electrolyte for green by changing the active element to be driven under the control of the driving IC, and repeating the same operation. Form a colored film. That is, a full-color colored film can be formed by repeating the immersion step and the electrodeposition step a plurality of times for a plurality of different transparent conductive films in this order using the electrolyte solution corresponding to each color.

The applied voltage for forming the colored film, that is, the potential difference between the anode and the cathode or the reference electrode in the case of the three-electrode arrangement is close to the drive voltage for driving the active element. A voltage, preferably an equivalent voltage, is good, and any voltage lower than the withstand voltage of the active element may be used. Specifically, the voltage is preferably 10 V or less, more preferably 4 V or less.
When the applied voltage exceeds 10 V, oxygen is generated as a gas on the transparent conductive film on which a colored film is to be formed, along with generation of a large amount of protons generated by electrolysis. In some cases, the colored film is peeled off at that portion, and irregularities and defoaming marks due to bubbles are formed, so that a colored film having a smooth surface cannot be formed. The above-mentioned reference electrode refers to another electrode generally used in the electrochemical field, except for an anode and a cathode of a device having a three-electrode arrangement of electrodes.

The current value when a voltage is applied to the transparent conductive film is preferably 0.3 to 50 mA / cm ² , and 0.3 to 50 mA / cm ^2.
10 mA / cm ² is more preferable. That is, when converted into one transparent conductive film (one pixel), the current value is 0.3 to 30 μA. The energizing time at the time of applying a voltage is proportional to the intensity of the applied current value, but is preferably 0.01 second to 1 hour, and more preferably 0.1 second to 10 minutes.

Next, the dispersion state of the ionic molecule having a hydrophobic domain and the pigment as the coloring material in the electrolytic solution, the pH change occurring in the vicinity of the substrate of the electrolytic solution, and the formation mechanism of the colored electrodeposition film accompanying the dispersion Will be described. FIG. 5 is a diagram schematically showing a state of pigment particles dispersed in water. FIG.
It is a figure which shows the liquid property immediately after applying a voltage between a light-transmitting conductive film as a positive electrode and a counter electrode not shown. FIG.
FIG. 3 is a diagram showing a state in which a carboxyl group of an ionic molecule has been hydrophobized and a colored film has been formed on a light-transmitting conductive film.

As shown in FIG. 5, the ionic molecules (electrodeposited material) each having a whisker-like shape and having a hydrophobic domain and a hydrophilic domain are oriented on the surface of the pigment particles to disperse the pigment particles in the electrolyte. The ionic molecules present alone in the electrolytic solution act as a matrix-forming substance of the colored film when the colored film is formed on the light-transmitting conductive film. Figure 5 represents the state in which no voltage is applied to the light transmissive conductive film, a hydrophilic group (e.g., carboxyl group) of the ionic molecules in this state, = R-COO ^- as an ion in solution It has been dissociated.

As shown in FIG. 6, when a light-transmitting conductive film is used as a positive electrode and a voltage is applied between the light-transmitting conductive film and a counter electrode (not shown), a positive charge is given to the conductive film, and a positive charge exists near the conductive film. The generated water causes an electrolysis reaction, and a reaction represented by the following equation occurs. H ₂ O → 2H ⁺ + 1 / 2O ₂ + 2e ^- The hydrogen ions generated by the above reaction increase the concentration of hydrogen ions near the conductive film to which the voltage is applied, and the degree of the increase increases as the vicinity of the electrode increases. The further away from the electrode the smaller, the pH changes accordingly. That is, a region where the hydrogen ion concentration in the electrolytic solution rapidly rises near the surface of the conductive film, that is, a high hydrogen ion concentration region (low pH region, acidic region) is generated partially, specifically or locally. When the areas having the same pH value are connected by a line, FIG.
Can be represented by a pH equivalent line shown in FIG. Conductive films near the generated hydrogen ions (protons) are hydrophilic groups of the ionic molecule, for example, ions dissociated = RCOO ^- bound ^{to, = RCOO - + H + →} = by reaction RCOOH, carboxyl group Becomes hydrophobic and the ratio of hydrophilic domains possessed by the ionic molecule decreases, and as shown in FIG. 7, a resin film (colored film, colored electrodeposition film) in which a pigment is incorporated on a light-transmitting conductive film Is formed.

Here, the hydrogen ions generated in the vicinity of the transparent electrode are successively connected to the dissociated anions of the ionic molecules in the electrolyte, and in this state, the reaction of depositing the ionic molecules on the transparent electrode is preferential. Proceed to In the method for forming a colored film of the present invention, a resin film in which a pigment is incorporated by a hydrogen ion exchange reaction based on a local change in the hydrogen ion concentration generated on the surface of the transparent electrode, that is, a local pH change is formed. However, the technical idea is different from that of the conventionally reported general electrophoresis-based electrodeposition. For example, in the present invention, the relationship between the voltage applied to the light-transmitting conductive film and the relative deposition rate on the conductive film surface is as shown in FIG. In the vicinity, electrolysis of water occurs, and at the same time, deposition of ionic molecules on the surface of the conductive film starts, and the deposition rate progresses in proportion to the applied voltage up to 3V. Conventionally, when electrodeposition is performed by an electrophoresis method, several tens to several hundreds of volts are required.
In this regard, it can be clearly distinguished from those requiring an applied voltage of.

As shown in FIG. 8, the relative deposition rate linearly increases to a voltage at which oxygen gas is generated (oxygen bubbling phenomenon) with generation of a large amount of hydrogen ions (protons) near the transparent electrode. . In the present invention, since film formation is performed between these voltages, oxygen gas does not occur as bubbles on the transparent conductive film on which the colored film is to be formed, and there is no film peeling or unevenness due to generation of bubbles during film formation. A colored film having a uniform thickness and excellent surface smoothness can be stably formed.

Next, FIG. 9- (1) and (2) show the relationship between the applied voltage and the relative amount of deposition. FIG. 9- (1) is an example of an electrodeposition material having a large hysteresis, and FIG. 9- (2)
Is an example of an electrodeposition material having a small hysteresis. In the electrodeposited material exhibiting the hysteresis, the applied voltage is gradually increased, and when the applied voltage exceeds a certain voltage (electrolysis starting potential), the amount of ionic molecules deposited rapidly increases, and thereafter the applied voltage gradually increases. Even when the amount of the electrodeposition material decreases, it has a characteristic that the relative adhesion amount of the electrodeposition material does not decrease. Such hysteresis is important for re-dissolving the ionic molecules in the electrolyte after forming the film, that is, for ensuring the retention of the formed film and preventing the quality from being deteriorated. It is preferable that the material exhibit hysteresis in a state change (dissolution state → change in precipitation and change in precipitation → dissolution state) corresponding to a change in pH.
That is, the change to the precipitation state corresponding to the decrease or increase of the pH is steep, and the change to the dissolved state corresponding to the increase or decrease of the pH is slow, and the stability of the colored electrodeposition film is improved. It is preferred. Local p generated near the transparent electrode
Specifically, the H drop is about 1 pH in the vicinity of the electrode.
２2, change in hydrogen ion concentration of about 10 ¹² to 10 ¹⁴ mol in terms of hydrogen ion concentration (increase in hydrogen ion concentration, p
H value).

In the electrolytic solution, in order to increase the electrodeposition speed,
An ion dissociating salt that does not affect the electrodeposition properties may be added, and the addition of the salt increases the conductivity of the solution. The conductivity in the aqueous liquid is correlated with the electrodeposition rate (in other words, the amount of electrodeposition). The higher the conductivity, the thicker the electrodeposition film deposited in a certain period of time, and the higher the conductivity. About 100mS /
When it reaches cm ² (corresponding to 10 Ω · cm), saturation is reached. Therefore, the electrodeposition rate can be controlled by adding ions that do not affect the formation of the colored electrodeposition film, such as Na ⁺ ions and Cl ⁻ ions, to the electrolyte. To adjust the volume resistivity of the electrolyte solution by the addition of the salt, the said volume ^{resistivity, 10 0 ~10 5 [Ω ·} c
m] is preferred.

After the step of forming a colored electrodeposition film of each color or the step of forming a black matrix described later, the substrate may be subjected to liquid cleaning in order to remove the electrolytic solution adhered to the substrate and used in each step. . As the cleaning liquid to be used, the same liquid as that usable in the first embodiment can be used.

[Hardening Step] As the hardening step in this embodiment, the same treatment as the hardening step in the first embodiment can be provided. By the hardening step, the film strength and solvent resistance of the formed film can be improved.

<Substrate> An electronic circuit material (TFT or the like) may be used as a substrate having a light-transmitting conductive film and an electronic circuit material bonded to the light-transmitting conductive film on a light-transmitting substrate. A substrate that can be driven to directly form a colored film by the driving voltage, for example, a driving element substrate configured as described below may be used. Here, the electronic circuit material refers to each electrode such as a gate electrode, a source electrode, and a drain electrode, an insulating film,
It refers to an active element or the like that is made by appropriately combining materials such as semiconductors and performs a switching function by being joined to a conductive film on the same base. When a liquid crystal material is used in combination, the liquid crystal display is controlled. For example, a thin film transistor (hereinafter simply referred to as “TF
T ". ) And the like.

That is, the configuration of the driving element substrate is not particularly limited. For example, (1) an active element having a source electrode, a drain electrode, a gate electrode and the like on the same substrate, A light-transmitting conductive film is provided later adjacent to the element, and the substrate in which the drain electrode is electrically coupled to the conductive film, or (2) a light-transmitting conductive film is formed over the same substrate. And an active element having a source electrode, a drain electrode, a gate electrode, and the like adjacent to the conductive film are arranged two-dimensionally in a matrix, and the source electrode is electrically coupled to the first common electrode; The substrate may be a substrate in which the gate electrode is coupled to the second common electrode, or more specifically, may be a substrate in which electronic circuit materials are arranged in the mode shown in FIG. In FIG. 10, the gate electrode 15 and the gate electrode 1 are formed on the same glass substrate.
A semiconductor 16 is stacked on the semiconductor layer 5 via an insulating film, and a drain electrode 17 is joined to the semiconductor 16. The drain electrode 17 is also joined to a light-transmitting conductive film provided on the base later, and further connected to the source electrode 18 via the semiconductor 16 with an electrode 18 ′.

The source electrode and the drain electrode are generally made of aluminum, molybdenum, copper, tantalum or the like, and the gate electrode is generally made of chromium, copper, aluminum, or the like.
It is made of molybdenum, tantalum or the like.

Hereinafter, an example of a method for forming a colored electrodeposition film (color filter film) according to this embodiment will be briefly described with reference to FIGS. First, the driving element having a thin film transistor (TFT) as an active element and a light-transmitting conductive film is prepared. That is, a substrate 2 such as glass
0, a gate electrode 15 and ITO (Indium-Ti
n-Oxide) light-transmitting conductive film 19 is formed,
Further, the semiconductor thin film 16 is placed via an insulating film (not shown).
Are laminated. These materials can be formed on the substrate 20 by a photolitho etching process typified by a thin film forming process such as vapor deposition, coating, resist film formation, and etching. In the same manner, the source electrode 1
8 ′, a drain electrode 17 is formed on the semiconductor thin film 16. At this time, the drain electrode 17 corresponding to each display pixel
Is formed so as to be electrically connected to the adjacent conductive film 3 correspondingly. Thus, the substrate 13 including the conductive film and the thin film transistor (TFT) can be manufactured.

Next, the conductive film 1 provided on the glass substrate
A colored electrodeposition film (color filter film) can be formed on 9 as follows. The base 20 provided with the individual TFTs and the conductive film 19 arranged in a matrix is electrically masked so that the conductive film 19 remains. This is because, in the electrodeposition step, the substrate 20 is brought into contact with or immersed in the electrolytic solution, and the working electrode 7 on the gate side (gate electrode 15 in FIG. 11) and the counter electrode 14 on the source side (source electrode 18 in FIG. 11). This is to prevent the TFTs corresponding to the respective display pixels from being short-circuited and the electrodes and the semiconductor thin film constituting the respective TFTs from being oxidized by contact with water when the current is supplied. In this case, also in this case, the counter electrode 14 and the working electrode 7 to which each TFT in each display pixel is connected also extend to the end of the base 20 while being insulated from contact with water. Preferably, it is connected to a TFT driving IC integrated with the base. The driving IC may be a thin film IC integrally formed on the base 1 by a thin film forming process. In this case, a thin film IC
Is connected to a power supply outside the substrate. In addition, the driving IC
May be a driving IC chip separately mounted on the end of the base or provided outside the base and connected to the counter electrode 14 and the working electrode 7.

Next, an apparatus having a structure similar to that of FIG. 14 was prepared. The electrodeposition tank 1 is filled with an aqueous electrolyte solution containing at least one of an ammonium compound and a salt thereof together with an electrodeposition material 2 and a pigment 3 of RGB corresponding to each hue. As an electrodeposition substrate, the substrate 13 having a conductive film and a thin film transistor (TFT) manufactured as described above was mounted so as to be immersed in an electrolytic solution. However, in this embodiment, it is not necessary to provide a light source.

In this state, by selectively controlling and driving the thin film transistors (TFTs) on the substrate 20 in a predetermined order, a voltage is selectively applied to the plurality of conductive films exposed in the electrolytic solution. Then, a current is supplied between the electrode and a counter electrode separately disposed in the electrodeposition liquid. On the electrically conductive film,
Uniform thickness, no air bubbles (Non-Bubbl
e), a colored film having excellent surface smoothness without irregularities or defoaming traces due to bubbles is formed, and by selectively applying a voltage by using an electrolytic solution corresponding to each color and repeating the energization, a TFT is formed.
In addition, a full-color filter film can be formed directly on a substrate provided with a conductive film.

As described above, the TF of the substrate provided with the conductive film and the TFT can be obtained without adversely affecting the operation characteristics of the TFT.
It is possible to stably form a high-resolution, uniform-thickness colored film having excellent surface smoothness without irregularities or defoaming marks due to bubbles by directly driving the T and using a driving voltage at the time of the driving. it can.

-Step of Forming Black Matrix- In the present invention, a step of forming a black matrix may be provided. In the black matrix forming step, by the same process as the above-described colored film forming step, light is irradiated using an aqueous electrolyte solution containing a black coloring material, and the light irradiated portion is selectively black colored film, that is, A black matrix may be formed. As an aqueous electrolyte,
A step of forming a metal plating thin film using an aqueous electrolyte containing a metal-containing electrodeposition material may be used. Alternatively, photolithography can be used. The black matrix forming step may be provided before the colored film forming step or may be provided after the colored film forming step.

The function of the black matrix layer is as follows.
Both light shielding properties and light reflection preventing properties are required. If the black matrix layer is not obtained as a thin film, it becomes difficult to form a fine pattern of the black matrix layer. That is, by forming a thin film having two functions such as high light transmissivity and absorption of incident light without reflection, high characteristics are exhibited. As described above, in order to form a black matrix layer that satisfies the high light-shielding ability of a metal thin film, the high light absorption of a black pigment-dispersed resin-based thin film, and the reduction in thickness, a metal thin film and a black pigment It is also possible to form a black matrix layer having a layer structure in which a dispersed resin-based thin film is composited (laminated).

Further, a solution of an ultraviolet curable resin containing a black coloring material such as black carbon powder is applied on the colored film formed on the substrate, or the substrate on which the colored film is formed is brought into contact with the solution. Then, a black matrix may be formed by irradiating ultraviolet rays to form a resin thin film containing a black coloring material.

As described above, in the case of a method using an aqueous electrolyte containing a black coloring material, the black coloring material includes:
Although a known black coloring material can be used as appropriate, from the viewpoint that the colored film can be formed to have an overlapping portion after forming a black matrix as described below,
A conductive black coloring material is preferable, and among them, carbon black is particularly preferable. In addition, the polymer material contained in the electrodeposition material is the same as the material used in the colored film forming step.

In the case of forming a metal plating thin film, an aqueous electrolytic solution containing an electrodeposition material containing a metal is used as the aqueous electrolytic solution. A black matrix composed of a metal plating thin film can be formed by the same process as the used black matrix forming step. In the upper layer on which the metal plating thin film is deposited, since the resistance of the metal film is low, the generated current is diffused and the electrodeposition film tends to be unnecessarily laminated, which is preferable in that the black matrix can be made thin.

When the metal plating thin film is provided before the colored film forming step, it is preferable that the metal plated thin film has resistance to the aqueous electrolyte used in the colored film forming step. Therefore, it is preferable to use, as the metal plating thin film, an aqueous electrolyte containing a metal having high robustness, such as Ni, Cr, Cu, Au, Ag, Mo, or the like.
Examples include Sn, Zn, Co, Ti, Ta, Pb, and Rr, and it is preferable to use an aqueous electrolyte containing one or more metal ions selected from these. Among them,
Ni, Cr, Cu, Au, Ag, Mo, Sn, Zn, C
The metal ion selected from o is particularly preferable in terms of the ability to form a thin film and the stability of the plating solution.

When a black matrix is formed by using a solution of an ultraviolet curable resin containing the black coloring material,
A black coloring material is dispersed in a solution in which an ultraviolet curable resin is dissolved in a solvent, and the black coloring material is attached to the entire surface of the substrate on which the colored film is formed, and only the region where the black matrix is formed is irradiated with ultraviolet light. And then dissolved in a solvent to remove the solution present in the uncured area.

In the case where a colored film and a black matrix are provided on a substrate, a black matrix or a mono-colored or multi-colored colored film is formed via a photomask in order to eliminate a gap between the colored film and the black matrix. It is preferable to form a monochromatic or multicolored colored film or a black matrix so as to overlap with the black matrix or the colored film. That is, when a colored film is formed after the formation of the black matrix, the colored film is formed also on the irradiated black matrix by irradiating light to the region of the black matrix so that a region overlapping with the black matrix is formed. Conversely, the same applies to the case where a black matrix is formed after forming a colored film.

As described above, it is preferable to provide a protective layer on the colored film and the black matrix formed on the substrate. Further, the surface of the protective layer may be subjected to an orientation treatment by a known method such as a rubbing treatment.

After the first and second steps (the step of forming a colored film of each color) or the step of forming a black matrix, which will be described later, to remove the electrolytic solution adhered to the substrate and used in each step, May be subjected to liquid washing. As a cleaning liquid to be used, a transparent and highly safe inert liquid is preferable. However, since the film is formed immediately after deposition, the formed film itself has low strength, so that a cleaning liquid that promotes solidification simultaneously with cleaning and removal is effective. It is more preferable to use a cleaning liquid that promotes solidification of the polymer film because the film strength of the polymer film is improved.

As the above-mentioned cleaning solution, the pH at which the electrodeposition material contained therein is more likely to precipitate than the pH value at which the electrolytic solution starts to precipitate is higher than that of the electrolyte solution.
H-based aqueous liquids are preferred. Such a p
When the substrate on which the polymer film (electrodeposited film) is formed is washed with the H-prepared solution, it is possible to remove the electrolytic solution and the like used in the previous step adhered to the substrate and to improve the film strength of the polymer film. Can be. By such washing, for example, when an electrodeposition material having an anionic dissociation group such as carboxyl group is used, the pH value of the cleaning solution is the pH at which the electrodeposition material starts to be deposited.
In the case of an electrodeposition material having a cationic dissociation group such as an amino group, which is lower than the pH value, the pH value of the cleaning solution is set higher than the pH value at the start of the deposition of the electrodeposition material, so that the robustness of the polymer film is improved. Can be improved.

[0129]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
All “%” in the examples represent “% by weight”. (Example 1) Styrene-acrylic acid-
An acrylic acid ester copolymer (molecular weight 10,000; hereinafter, abbreviated as “SAAE”) is used as an aqueous solvent (dissolving material) for dissolving the electrodeposition material, 500 g of a 10% aqueous solution of tetraethylammonium hydroxide (ammonium). A compound salt-containing solvent, pH 14.45 or less, manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter, abbreviated as "TEAOH") was prepared.

SAAE5 in 500 g of the TEAOH
After adding 0 g and stirring for about 20 minutes, all were dissolved. Further, 50 g of SAAE is added to T in which SAAE is dissolved.
It was put in EAOH and stirred for 30 minutes to completely dissolve. Again, 50 g of SAAE was added to TEAOH in which SAAE was dissolved, and stirred for 40 minutes to dissolve. Then, add SA
The amount of AE added was reduced to 30 g, 30 g of SAAE was further added, and the mixture was shaken for about 10 minutes, and then stirred for about 1 hour to dissolve almost all of the AE.
A 0% resin solution was prepared. Then, another 20 g of S
Add AAE to the solution and shake for about 10 minutes.
Thereafter, the mixture was stirred for about 3 hours to prepare a resin solution having a solid content of about 35%. The pH at this time was 7.8.

Subsequently, water was added to the obtained resin solution having a solid content of about 35% to dilute the solution to a resin solution having a solid content of 10%. In order to impart conductivity to 25 ml of the resin solution having a solid content of 10% and adjust the pH to an acidic side,
7 ml of a 1 mol / L ammonium chloride aqueous solution was added,
An aqueous electrolyte having a pH of 7.75 was obtained. The conductivity of the aqueous electrolyte was 50.3 mS. As described above, a large amount of electrodeposition material could be dissolved, and an aqueous electrolyte having a low pH value could be prepared.

Example 2 Instead of the ammonium compound salt-containing solvent used in Example 1, a 10% aqueous solution of tetramethylammonium hydroxide (pH of about 16.0 or less,
Tokyo Chemical Industry Co., Ltd .; hereinafter abbreviated as "TMAOH". ) Was performed in substantially the same manner as in Example 1 except that
The AAE resin was dissolved to prepare an aqueous electrolyte having a pH of 7.6 and a solid content of 30%. As mentioned above, pH
An aqueous electrolyte having a low value could be obtained.

Comparative Example 1 A SAAE resin was dissolved in substantially the same manner as in Example 1 except that an aqueous KOH solution was used in place of the ammonium compound salt-containing solvent used in Example 1, and the pH was 7.9. A resin solution having a solid content of 30% was prepared. As described above, an aqueous electrolyte having a low pH value could not be obtained.

(Example 3) An electrodeposition tank filled with the aqueous electrolyte solution obtained in Example 1 was prepared so as to have the same configuration as that shown in FIG. 12, and a counter electrode 6 was placed in the electrodeposition tank. The working electrode 7 was immersed in the electrodeposition substrate 4 on which the ITO thin film (conductive film) was formed, and the reference electrode 5 was placed in another solution tank. The electrodeposition substrate 4 is connected to a power source via a working electrode 7 connected to an ITO thin film. The aqueous electrodeposition liquid includes an electrodeposition material 2 and a pigment (or a pigment containing a dispersing resin) 3. In this embodiment, no light source is provided. When a voltage of 2.2 V is applied between the counter electrode 6 and the working electrode 7, about 3
After 0 seconds, a 0.5 μm polymer film (electrodeposited film) was formed. Even if the voltage application is stopped after the polymer film is formed,
No re-dissolution of the polymer film was observed, and a strong polymer film having a smoother film surface could be formed.

(Embodiment 4) In contrast to the apparatus (FIG. 12) constructed in the same manner as in the embodiment 3, the electrodeposition tank 1 was constructed so as to be transparent.
A light source was arranged outside the electrodeposition tank 1 at a position where light could be irradiated to the electrodeposition substrate 4 in the direction indicated by the arrow in the figure. Instead of the electrodeposition substrate 4 used in Example 3, ITO was
Example 2 except that the substrate and the TiO ₂ film were laminated in this order, and the substrate was irradiated with light in the direction of the arrow while applying a bias voltage of 2.0 V between the counter electrode 6 and the working electrode 7. Operating in the same manner as in Example 3, 0.5 μm
m was formed. Even if the application of the voltage is stopped after the polymer film is formed, re-dissolution of the polymer film is not observed, and the application of a lower voltage may form a smoother and stronger polymer film on the film surface. did it.

(Example 5) An apparatus having a counter electrode made of a platinum plate having the same area as the electrodeposition substrate and having the same configuration as that shown in FIG. 13 was prepared, and the electric field between the counter electrode 10 and the working electrode 4 was equal. The operation was carried out in the same manner as in Example 3 except that a voltage was applied so as to be as follows. Then 0.5μ
m could be formed. Even after the application of the voltage was stopped after the formation of the polymer film, the polymer film was not re-dissolved, and a polymer film having a smoother and stronger film surface could be formed.

Example 6 The drive element substrate having a thin film transistor (TFT) element as an active element and a light-transmitting conductive film was prepared. That is, as shown in FIG. 14, after a gate electrode 15 and an ITO film 19 were formed on a substrate 20 such as glass by photolithography, a semiconductor thin film 16 was further laminated via an insulating film (not shown). . In the same manner, a source electrode 18 ′ and a drain electrode 17 are formed on the semiconductor thin film 16 so as to be electrically connected to the conductive film 3, and the electrodeposition substrate 13 having the conductive film and the TFT element is formed. Was prepared.

An apparatus similar to that of FIG. 12 used in Example 5 was prepared, and the electrodeposition substrate 1 obtained above was used in place of the electrodeposition substrate 4.
3 was immersed in an aqueous electrolyte solution. The counter electrode 14 is connected to the source side of the substrate 13 and the working electrode 7 is connected to the gate side.
By applying a minute amount, a polymer film could be formed on the conductive film 3 serving as a pixel electrode on the substrate 13. As described above,
Even when a substrate provided with a TFT element is immersed in an aqueous electrolyte to form a film, a polymer film having high resolution and excellent pattern accuracy is stably formed without impairing the operation characteristics of the TFT element. We were able to. Further, even when the application of the voltage was stopped after the formation of the polymer film, the polymer film was not redissolved, and a polymer film having a smoother and stronger film surface could be formed.

[0139]

According to the present invention, a high-resolution and high-precision pattern can be directly formed on a substrate provided with an electronic circuit material without considering the adverse effect on the operating characteristics of the electronic circuit material such as a TFT element. A molecular film can be formed stably. When a color material such as a pigment is included, a color filter film having high resolution and excellent pattern accuracy can be stably formed directly on a substrate provided with an electronic circuit material. Further, according to the present invention, the pigment dispersibility in an aqueous electrolyte solution can be further improved, and the re-dissolution phenomenon of the formed polymer film can be effectively prevented, the concentration uniformity is excellent, and the smoothness is improved. And a strong polymer film can be formed.

[Brief description of the drawings]

FIG. 1 is a diagram showing an energy band of an optical semiconductor having a Schottky junction.

FIG. 2 is a diagram showing an energy band of an optical semiconductor having a pin junction.

FIG. 3 is a schematic sectional view showing the structure of a light-transmitting n-type semiconductor.

FIG. 4 is a diagram showing a configuration example of a substrate provided with an electronic circuit material.

FIG. 5 is a view schematically showing a state of pigment particles dispersed in water.

FIG. 6 is a diagram showing liquid properties immediately after a voltage is applied between a light-transmitting conductive film as a positive electrode and a counter electrode (not shown).

FIG. 7: The carboxyl group of the ionic molecule becomes hydrophobic,
FIG. 3 is a diagram illustrating a state in which a colored film is formed on a light-transmitting conductive film.

FIG. 8 is a diagram showing the relationship between the applied voltage and the deposition speed during electrodeposition.

FIG. 9 is a diagram showing the formation characteristics of a colored film with respect to an applied voltage at the time of electrodeposition.

FIG. 10 is a diagram illustrating an example of a configuration of an electronic circuit material.

FIG. 11 is a plan view showing a specific mode of an electronic circuit material.

FIG. 12 is a diagram illustrating an example of a method for forming a polymer film of the present invention.

FIG. 13 is a diagram illustrating an example of a method for forming a polymer film according to the present invention.

FIG. 14 is a diagram illustrating an example of a method for forming a polymer film of the present invention using a substrate provided with an electronic circuit material.

[Explanation of symbols]

1 electrodeposited layer 2 electrodeposition material 3 colorant (pigment) 4 substrate (if light irradiation, TiO ₂ / ITO laminated board) substrate 14 source having a 5 Reference electrode 6, 10 counter electrode 7 working electrode 13 electronic circuit material Electrode 31 Optical semiconductor thin film 32 Conductive film 33 Substrate 34 Electronic circuit material

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keiji Shimizu 430 Nakai-cho, Nakai-cho, Ashigara-gun, Kanagawa Prefecture Inside Fuji Xerox Fuji Xerox Co., Ltd. In-house F term (reference) 2H048 BA62 BB02 BB43 BB47 2H091 FA02Y FB12 FC06 FD04 FD24 GA13 LA15

Claims (22)

[Claims] A first step of bringing a conductive substrate into contact with an aqueous electrolyte solution containing an electrodeposition material; and a step of electrochemically depositing the electrodeposition material on the substrate by changing a hydrogen ion concentration. Forming a polymer film, comprising: a second step of forming an electrodeposition film, wherein the aqueous electrolyte solution contains at least one of an ammonium compound and a salt thereof. Method. 2. The method according to claim 1, wherein the ammonium compound is an ammonium or organic ammonium compound. 3. The method according to claim 2, wherein the organic ammonium compound is a tetraalkylammonium compound. 4. The method according to claim 3, wherein the salt of the tetraalkylammonium compound is a tetraalkylammonium hydroxide. 5. The method for forming a polymer film according to claim 3, wherein the alkyl group of the tetraalkylammonium compound or a salt thereof is a methyl group or an ethyl group. 6. The method for forming a polymer film according to claim 1, wherein the aqueous electrolyte further contains a coloring material, and the colored electrodeposition film is formed in the second step. 7. The method according to claim 1, wherein the first step comprises: laminating at least a light-transmitting conductive film and a light-transmitting optical semiconductor thin film having a photovoltaic function on a light-transmitting substrate in this order. A step of bringing the semiconductor thin film into contact with an aqueous electrolyte containing an electrodeposition material containing a coloring material, wherein the second step is to irradiate the substrate with light in an aqueous electrolyte, 7. The method for forming a polymer film according to claim 6, wherein a step of selectively generating a photoelectromotive force and electrochemically depositing the electrodeposition material to form a colored electrodeposition film. 8. The method according to claim 7, wherein the substrate further comprises an electronic circuit material. 9. The method according to claim 1, wherein the first step comprises: forming a light-transmitting substrate on a light-transmitting substrate and at least the light-transmitting conductive film and an electronic circuit material bonded to the light-transmitting conductive film. Contacting an aqueous conductive solution with an aqueous electrolyte solution containing an electrodeposition material containing a coloring material, and the second step is to transfer the electronic circuit material of the substrate to the aqueous electrolyte solution with the light-transmitting conductive material. By driving in a state where the membrane is in contact, a voltage is generated in the light-transmitting conductive film, where an aqueous electrolyte is electrolyzed to generate hydrogen ions and no bubbles which substantially reduce the film-forming property. 7. A step of applying a pressure to deposit an electrodeposition material on the light-transmitting conductive film to form a colored electrodeposition film.
3. The method for forming a polymer film according to 1. 10. The method for forming a polymer film according to claim 7, wherein the optical semiconductor thin film contains a titanium oxide-based compound as a main component. 11. The method for forming a polymer film according to claim 6, wherein the coloring material is a pigment, and the number average particle diameter of the pigment is 0.2 to 200 nm. 12. The method according to claim 1, wherein the electrodeposition material contains a compound having a carboxyl group. 13. The compound according to claim 12, wherein the compound having a carboxyl group is a polymer having a hydrophobic domain and a hydrophilic domain, and the number of the hydrophobic domains is 30 to 85% of the total number of the hydrophobic domains and the hydrophilic domains. A method for forming a polymer film. 14. The polymer is a copolymer of a hydrophobic domain having a styrene structure or a substituted styrene structure and a hydrophilic domain, and the number of hydrophobic domains is 55 to 85% of the total number of hydrophobic domains and hydrophilic domains. The method for forming a polymer film according to claim 13, wherein 15. The method for forming a polymer film according to claim 13, wherein the polymer is a styrene-acrylic acid-acrylate copolymer. 16. The method for forming a polymer film according to claim 13, wherein the acid value of the polymer is 60 to 200. 17. The method according to claim 17, wherein at least 50% of the number of hydrophilic domains of the polymer is changed from water-soluble to water-insoluble due to a change in pH, or
The method for forming a polymer film according to any one of claims 13 to 16, wherein the method can change reversibly. 18. The polymer having a number average molecular weight of 6,000 to 6,000.
The method for forming a polymer film according to any one of claims 13 to 17, wherein the molecular weight is 25,000. 19. The method according to claim 1, wherein the pH of the aqueous electrolytic solution is within a range of ± 2.5 of a pH value at which the electrodeposition material starts to precipitate and is 8.5 or less. Method of forming molecular film. 20. The method for forming a polymer film according to claim 1, wherein ammonium chloride is used as a pH adjuster for the aqueous electrolyte solution. 21. The method for forming a polymer film according to claim 1, wherein the aqueous electrolyte contains a conductive material. 22. The content of the aqueous solvent in the aqueous electrolyte solution is as follows:
The amount is 65 to 96% by weight of the total weight of the aqueous electrolyte.
22. The method for forming a polymer film according to any one of the above items.